In Situ X-ray Absorption Spectroscopy Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction

In situ X-ray absorption spectroscopy (XAS) is a powerful technique that can be applied to electrochemical systems, with the ability to elucidate the chemical nature of electrocatalysts under reaction conditions. In this study, we perform in situ XAS measurements on a bifunctional manganese oxide (MnOx) catalyst with high electrochemical activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Using X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), we find that exposure to an ORR-relevant potential of 0.7 V vs RHE produces a disordered Mn3(II,III,III)O4 phase with negligible contributions from other phases. After the potential is increased to a highly anodic value of 1.8 V vs RHE, relevant to the OER, we observe an oxidation of approximately 80% of the catalytic thin film to form a mixed Mn(III,IV) oxide, while the remaining 20% of the film consists of a less oxidized phase, likely corresponding to unchanged Mn3(II,III,III)O4. XAS and electrochemical characterization of two thin film catalysts with different MnOx thicknesses reveals no significant influence of thickness on the measured oxidation states, at either ORR or OER potentials, but demonstrates that the OER activity scales with film thickness. This result suggests that the films have porous structure, which does not restrict electrocatalysis to the top geometric layer of the film. As the portion of the catalyst film that is most likely to be oxidized at the high potentials necessary for the OER is that which is closest to the electrolyte interface, we hypothesize that the Mn(III,IV) oxide, rather than Mn3(II,III,III)O4, is the phase pertinent to the observed OER activity.